US4599391A - Coating composition for power cable - Google Patents
Coating composition for power cable Download PDFInfo
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- US4599391A US4599391A US06/682,910 US68291084A US4599391A US 4599391 A US4599391 A US 4599391A US 68291084 A US68291084 A US 68291084A US 4599391 A US4599391 A US 4599391A
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- Prior art keywords
- copolymer
- ethylene
- power cable
- composition
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- 239000008199 coating composition Substances 0.000 title claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 29
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000005977 Ethylene Substances 0.000 claims abstract description 17
- 238000004132 cross linking Methods 0.000 claims abstract description 15
- 150000002978 peroxides Chemical class 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000004711 α-olefin Substances 0.000 claims abstract description 12
- 238000000113 differential scanning calorimetry Methods 0.000 claims abstract description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 10
- 239000011630 iodine Substances 0.000 claims abstract description 10
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 9
- 150000001993 dienes Chemical class 0.000 claims abstract description 9
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 7
- 239000000155 melt Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000009413 insulation Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 4
- 238000007765 extrusion coating Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 229920001038 ethylene copolymer Polymers 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 30
- 229920001684 low density polyethylene Polymers 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 9
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 8
- 239000004702 low-density polyethylene Substances 0.000 description 8
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 7
- -1 polyethylene Polymers 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920002959 polymer blend Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011953 free-radical catalyst Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- PPWUTZVGSFPZOC-UHFFFAOYSA-N 1-methyl-2,3,3a,4-tetrahydro-1h-indene Chemical compound C1C=CC=C2C(C)CCC21 PPWUTZVGSFPZOC-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical group COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- DOMHCBYZLIWUHE-UHFFFAOYSA-N 2-(chloromethyl)-3-prop-1-en-2-ylbicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(C(=C)C)C2CCl DOMHCBYZLIWUHE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 1
- UGJBFMMPNVKBPX-UHFFFAOYSA-N 5-propan-2-ylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C(C)C)CC1C=C2 UGJBFMMPNVKBPX-UHFFFAOYSA-N 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/083—Copolymers of ethene with aliphatic polyenes, i.e. containing more than one unsaturated bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Definitions
- the present invention relates to a power cable coating composition capable of affording an insulation coating superior in heat resistance.
- olefinic polymers are superior in various characteristics, including electrical and mechanical characteristics and chemical stability. Above all, low density polyethylenes prepared by a high pressure process radical polymerization are inexpensive, exhibit a reduced dielectric loss, are superior in processability, can be greatly improved in heat resistance by crosslinking, and are less likely to exhibit a tree phenomenon induced by incorporation of a foreign matter such as a residual catalyst as compared with polymers prepared by ionic polymerization. Because of these various advantages, olefinic polymers are in wide use as insulating materials for electric wires and power cables.
- ethylene copolymer rubber alone or in combination with low density polyethylenes has also been proposed as a coating material in characteristics such as the resistance to dielectric deterioration as compared with a single use of polyethylene, but the heat resistance of crosslinked polyethylene is deteriorated by the incorporation of ethylene copolymer rubber. And in the use of ethylene copolymer rubber alone, deterioration results not only in heat resistance but also in various other characteristics such as resistance to oil, to ozone and to wear.
- the present invention resides in a power cable coating composition
- a power cable coating composition comprising a copolymer of ethylene or ethylene and an ⁇ -olefin with 0.02-2 mol % of a cyclic non-conjugated diene, prepared by a high-pressure radical polymerization process, said copolymer having a melt index of 0.2-10 g/10 min and an iodine value in the range of 0.2 to 20, and not more than 2.5 parts by weight, based on 100 parts by weight of said copolymer, of a peroxide, said composition on heat-crosslinking affording a crosslinked product having at least the following properties:
- Tm a maximum peak temperature (Tm) not lower than 100° C. measured according to the differential scanning calorimetry (DSC).
- Tm a maximum peak temperature (Tm) not lower than 100° C. measured according to the differential scanning calorimetry (DSC).
- the insulation coating layer will become fluidized and deformed at a high temperature above the melting point, for example, in the event of short-circuiting of the cable, thus resulting in deterioration of its electrical characteristics.
- the insulating layer will be fluidized and become thick locally at the service temperature of the cable, thus also resulting in deterioration of its electrical characteristics.
- the power cable insulating coating it is essential for the power cable insulating coating to have both the above heat-resisting properties (a) and (b).
- the present invention employs a specific, highly crosslinkable ethylene copolymer and a relatively small amount of peroxide, whereby the heat resistance of the resultant coating can be improved.
- the above ethylene copolymer which forms the power cable coating composition is a copolymer of ethylene or ethylene and an ⁇ -olefin with 0.02-2 mol % of a cyclic non-conjugated diene, prepared according to a high-pressure radical polymerization process.
- the ethylene copolymer may be used as a polymer blend containing said copolymer as a main component (hereinafter, both are referred to simply as "ethylene copolymer").
- Preferred examples of the ⁇ -olefin as a constituent of the ethylene copolymer are those having 3 to 12 carbon atoms such as propylene, butene-1, pentene-1, hexene-1, 4-methyl-pentene-1, octene-1, decene-1, vinyl acetate, ethyl acrylate, and mixtures thereof.
- the ⁇ -olefin content of the ethylene copolymer is in the range of 0 to 3 mol %, preferably not more than 1 mol %.
- cyclic non-conjugated diene in the copolymer mention may be made of the following: cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, alkenyl norbornenes such as 5-vinyl-2-norbornene, alkylidene norbornenes such as 5-ethylidene-2-norbornene, 5-methylene-2-norbornene and 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, divinylbenzene, norbornadiene, alkenylcyclohexenes such as 4-vinylcyclohexene. Particularly, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene and 4-vinylcyclohexene are preferred.
- the cyclic non-conjugated diene is copolymerized in an amount in the range of 0.02 to 2 mol % with ethylene or ethylene and ⁇ -olefin. If its amount is smaller than 0.02 mol %, the crosslinkability of the copolymer will be poor and the gel percentage low, thus resulting in deterioration of the heat resistance. And if its amount exceeds 2 mol %, the crystallinity of the copolymer will deteriorate and its melting point lower, thus resulting in lowering of the cable service temperature.
- the ethylene copolymer may be prepared by contacting and polymerizing the monomers simultaneously or in steps in a reaction vessel or tube in the presence of a free radical catalyst and a chain transfer agent and if necessary an auxiliary agent at a temperature of 50° to 400° C., preferably 100° to 300° C., and at a pressure of 500 to 4,000 kg/cm 2 , preferably 1,000 to 3,500 kg/cm 2 .
- free radical catalyst there may be used a known initiator.
- examples are peroxides, hydroperoxides, azo compounds, amine oxide compounds and oxygen.
- chain transfer agent examples include hydrogen, propylene, C 1 -C 20 or more saturated aliphatic hydrocarbons and halogen-substituted hydrocarbons, e.g. methane, ethane, propane, butane, isobutane, n-hexane, n-heptane, cycloparaffins, chloroform and carbon tetrachloride, C 1 -C 20 or more saturated aliphatic alcohols, e.g. methanol, ethanol, propanol and isopropanol, C 1 -C 20 or more saturated aliphatic carbonyl compounds, e.g. carbon dioxide, acetone and methyl ethyl ketone, as well as aromatic compounds such as toluene, diethylbenzene and xylene.
- saturated aliphatic hydrocarbons e.g. methane, ethane, propane, butane, isobutane, n-hexane,
- the density of the ethylene copolymer is usually in the range of 0.92 to 0.94 g/cc.
- the ethylene copolymer have an iodine value in the range of 0.2 to 20. If the iodine value is less than 0.2, the copolymer will be poor in crosslinkability, incapable of affording a power cable insulating coating superior in heat resistance. And if the iodine value exceeds 20, the melting point will lower remarkably, thus leading to a deteriorated heat resistance at the cable service temperature.
- the melt index (hereinafter referred to simply as "MI") of the ethylene copolymer is in the range of 0.2 to 10 g/10 min, preferably 0.3 to 8 g/10 min. If MI is less than 0.2 g/10 min, there will occur heat generation, scorch, unevenness of flow or shark skin during extrusion, and if MI exceeds 10 g/10 min, there will occur processing troubles such as sag and local increase in thickness of the resin, thus resulting in deteriorated characteristics of the power cable insulating coating obtained.
- the polymer to be blended therewith include other ethylene polymers, e.g. high-, medium- and low-density polyethylenes, copolymers of ethylene and C 3 -C 10 ⁇ -olefins, and copolymers of ethylene and monomers having polar groups such as vinyl acetate, acrylic acid, acrylic acid ester and methacrylic acid ester.
- the blending ratio it is desirable that not less than 60 wt. %, more preferably, nor less than 70 wt. % of the ethylene copolymer be contained in the polymer blend.
- the peroxide used in the present invention is a known organic peroxide. Examples are dicumyl peroxide, tert-butyl dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3.
- the peroxide is used in an amount not more than 2.5 parts by weight based on 100 parts by weight of the coating composition, whereby there can be obtained an insulation coating having the properties previously described.
- the lower limit of its amount can be determined in the range in which such properties are attainable. But, usually and preferably, the lower limit is one part by weight.
- the insulation coating of the present invention has an improved heat resistance is presumed to be as follows. Because of use of the ethylene copolymer with plural unsaturated bonds introduced without lowering of crystallinity, the presence of unsaturated portion of the ethylene copolymer will increase the degree of crosslinking (gel percentage) and the crosslinking speed, thus resulting in improvement of both heat resistance and productivity.
- the application of the coating composition onto a cable can be done by a conventional method involving extrusion coating of the composition onto a travelling cable conductor or the like. Then, the composition is crosslinked by steam heating, induction heating or other suitable means, whereby there can be obtained a power cable having an insulation coating.
- the conditions for these operations are not specially limited.
- additives such as an anti-aging agent, a flame retardant, a voltage stabilizer, a copper damage preventing agent and carbon black, as well as rubber and filler in the range not departing from the gist of the present invention.
- the use of only a small amount of peroxide can afford a highly heat-resistant insulation coating on power cable because there is used the specific ethylene copolymer superior in crosslinking properties such as crosslinking speed and crosslinking degree (gel percentage). Further, heat generation and scorch during extrusion are reduced to a remarkable extent and it becomes possible to attain speed-up, that is, the productivity can be improved, which is economical.
- Ethylene and 5-vinyl-2-norbornene were polymerized in an autoclave at the temperature of 170° C. and pressure of 1,700 kg/cm 2 for 60 minutes in the presence of di-tert-butyl peroxide (polymerization initiator) and propylene (chain transfer agent), to obtain ethylene copolymers as shown in Table 1.
- Maximum peak temperature (Tm) measured according to DSC, percent heat-deformation, gel percentage and appearance were evaluated as set out in the same table.
- Ethylene copolymers were prepared under the same conditions as in Example 1 except that the comonomer content and MI were changed outside the scope of the present invention, followed by evaluation in the same way as in Example 1, results of which are as set out in Table 1.
- Ethylene copolymers were prepared under the same conditions as in Example 1 except that the kind of comonomer and MI were changed, followed by evaluation in the same way as in Example 1, results of which are as set out in Table 1.
- Example 1 70 parts by weight of the ethylene copolymer prepared in Example 1 was kneaded with 30 parts by weight of a commercially available high-pressure process low density polyethylene (trade name: Rexlon W3100, a product of Nippon Petrochemicals Co., Ltd.) (hereinafter referred to as "LDPE") for power cable by means of a plastograph, followed by evaluation in the same manner as in Example 1, results of which are as set out in Table 1.
- LDPE high-pressure process low density polyethylene
- Example 2 Polymerization was conducted under the same conditions as in Example 1 except that n-hexane was used in place of propylene as the chain transfer agent, to obtain an ethylene copolymer having such physical properties as shown in Table 1. Then, evaluation was made in the same way as in Example 1, results of which are as set out in the same table.
- Example 1 Polymerization was conducted under the same conditions as in Example 1 to obtain an ethylene copolymer having such physical properties as shown in Table 1, to which was added 1.5 parts by weight of peroxide. Then, evaluation was made in the same way as in Example 1, results of which are as set out in Table 1.
- Example 9 Polymerization was conducted under the same conditions as in Example 9 to obtain an ethylene copolymer having a relatively large comonomer content, followed by evaluation in the same way as in Example 1, results of which are as set out in Table 1.
- Example 11 An ethylene copolymer was prepared under the same conditions as in Example 11 except that the comonomer content was changed outside the scope of the present invention, followed by evaluation in the same way as in Example 1, results of which are as set out in Table 1.
- Examples 1-10 indicate that the percent heat-deformation is low and the gel percentage is high in comparison with conventional high-pressure process low density polyethylenes.
- the ethylene copolymers prepared using 5-vinyl-2-norbornene as comonomer afforded very goods results.
- Example 8 Similar effects were obtained even when there was used a blend of the ethylene copolymer with the commercial high-pressure process low density polyethylene.
- Comparative Examples 2 and 3 there were used ethylene copolymers having MI values outside the scope of the present invention.
- the resultant products exhibited conspicuous surface roughening or drawdown, and their values as product were badly deteriorated.
- Tm Maximum peak temperature measured according to Differential Scanning Calorimetry
- This temperature (Tm) is a value correlated with the crystal form and is measured in the following manner. About 5 mg. of sample is weighed and then set to DSC. The temperature is raised to 170° C. and the sample is held at this temperature for 15 minutes, then cooled to 0° C. at a rate of 2.5° C./min. Then, from this state the temperature is raised to 170° C. at a rate of 10° C./min. The temperature in the vertex position of the maximum peak appeared during the rise of temperature from 0° to 170° C. is regarded as the maximum peak temperature (Tm).
- a cylinder 10 mm in diameter and 6 mm in height is placed upright in an oil bath at 120° C. Then, a metallic plate is put thereon and pressurized from above at a load of 2.64 kg. After 30 minutes, the height of the cylinder is measured to determine a percent reduction in height, which is regarded as the percent heat-deformation.
- ethylene copolymer 100 parts by weight of the ethylene copolymer are added a predetermined amount of DCP (dicumyl peroxide) and 0.2 part by weight of 4,4'-thiobis(2-t-butyl-5-methylphenol), from which a 1 mm thick sheet is formed. After crosslinking at 160° C. for 30 minutes, the sheet is pulverized to pass through 20 mesh, then extracted with xylene at 120° C. for 10 hours and a percent retention is determined as the gel percentage.
- DCP dicumyl peroxide
- 4,4'-thiobis(2-t-butyl-5-methylphenol) 0.2 part by weight of 4,4'-thiobis(2-t-butyl-5-methylphenol
- the coating composition is extruded at the same shear rate as in power cable coating, and the extruded surface state is observed with the eye.
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Abstract
Description
TABLE 1 __________________________________________________________________________ Examples and Kind of Comonomer Comparative Examples (part of weight of copolymer) __________________________________________________________________________ Example 1 5-vinyl-2-norbornene (100) Example 2 " Example 3 " Example 4 " Example 5 5-ethylidene-2-norbornene (100) Example 6 " Example 7 4-vinylcyclohexene (100) Example 8 5-vinyl-2-norbornene (70) Example 9 5-vinyl-2-norbornene (100) Example 10 " Example 11 " Comparative Example 1 " Comparative Example 2 " Comparative Example 3 " Comparative Example 4 " Comparative Example 5 -- Comparative Example 6 -- __________________________________________________________________________ Physical Properties of Resin Amount of Examples and LDPE Comonomer MI peroxide Comparative (part by content (g/ Density Iodine added (part Examples weight) (mol %) 10 min) (g/cc) value by weight) __________________________________________________________________________ Example 1 -- 0.1 6.1 0.922 1 2 Example 2 -- 0.1 2.9 0.923 1 2 Example 3 -- 0.05 3.1 0.923 0.5 2 Example 4 -- 0.3 2.8 0.922 3 2 Example 5 -- 0.1 0.3 0.922 1 2 Example 6 -- 0.1 2.8 0.922 1 2 Example 7 -- 0.1 3.0 0.923 1 2 Example 8 LDPE 0.07 5.2 0.922 0.7 2 (30) Example 9 -- 0.07 3.1 0.930 0.7 2 Example 10 -- 0.1 2.8 0.923 1 1.5 Example 11 -- 1.8 5.0 0.930 18 2 Comparative -- 0.01 3.0 0.922 0.1 2 Example 1 Comparative -- 0.1 0.1 0.922 1 2 Example 2 Comparative -- 0.1 11 0.922 1 2 Example 3 Comparative -- 3.0 7 0.929 30 2 Example 4 Comparative LDPE 0 3.0 0.922 0 2 Example 5 (100) Comparative LDPE 0 3.0 0.922 0 3 Example 6 (100) __________________________________________________________________________ Physical Properties of Resin after Crosslinking Examples and Percent heat- Gel Comparative DSC (Tm) deformation percentage Appearance Examples (°C.) (%) (%) surface state __________________________________________________________________________ Example 1 103 9 88 Very smooth surface Example 2 103 7 90 Very smooth surface Example 3 104 13 86 Very smooth surface Example 4 102 6 91 Very smooth surface Example 5 104 14 85 Very smooth surface Example 6 105 19 82 Very smooth surface Example 7 103 11 87 Very smooth surface Example 8 103 10 87 Very smooth surface Example 9 110 12 86 Very smooth surface Example 10 105 19 82 Very smooth surface Example 11 101 3 96 Very smooth surface Comparative 105 34 74 Very smooth Example 1 surface Comparative 102 7 90 Surface roughening Example 2 is conspicuous Comparative 104 12 86 Drawdown is Example 3 conspicuous Comparative 95 3 97 Very smooth Example 4 surface Comparative 105 34 74 Very smooth Example 5 surface Comparative 103 15 84 Scorch occurred, Example 6 and surface rough- ening is conspi- cuous __________________________________________________________________________
Claims (6)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58238838A JPS60133042A (en) | 1983-12-20 | 1983-12-20 | Resin composition for electrically insulating use |
JP58-238838 | 1983-12-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
US4599391A true US4599391A (en) | 1986-07-08 |
Family
ID=17036023
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/682,910 Expired - Fee Related US4599391A (en) | 1983-12-20 | 1984-12-18 | Coating composition for power cable |
Country Status (4)
Country | Link |
---|---|
US (1) | US4599391A (en) |
EP (1) | EP0150610B1 (en) |
JP (1) | JPS60133042A (en) |
DE (1) | DE3477861D1 (en) |
Cited By (28)
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US5179171A (en) * | 1985-05-24 | 1993-01-12 | Mitsui Petrochemical Industries, Ltd. | Random copolymer, and process for production thereof |
US5395471A (en) * | 1991-10-15 | 1995-03-07 | The Dow Chemical Company | High drawdown extrusion process with greater resistance to draw resonance |
US5468819A (en) * | 1993-11-16 | 1995-11-21 | The B.F. Goodrich Company | Process for making polymers containing a norbornene repeating unit by addition polymerization using an organo (nickel or palladium) complex |
US5582923A (en) * | 1991-10-15 | 1996-12-10 | The Dow Chemical Company | Extrusion compositions having high drawdown and substantially reduced neck-in |
US5654386A (en) * | 1986-05-27 | 1997-08-05 | Mitsui Petrochemical Industries, Ltd. | Random copolymer, and process for production thereof |
US5658998A (en) * | 1985-05-24 | 1997-08-19 | Mitsui Petrochemical Industries, Ltd. | Random copolymer, and process and production thereof |
US5674342A (en) * | 1991-10-15 | 1997-10-07 | The Dow Chemical Company | High drawdown extrusion composition and process |
US5674613A (en) * | 1995-06-14 | 1997-10-07 | Exxon Chemical Patents Inc. | Electrical devices including ethylene, a-olefin, vinyl norbornene elastomeric polymers |
US5677405A (en) * | 1995-05-24 | 1997-10-14 | The B.F. Goodrich Company | Homopolymers and copolymers of cationically polymerizable monomers and method of their preparation |
US5747594A (en) | 1994-10-21 | 1998-05-05 | The Dow Chemical Company | Polyolefin compositions exhibiting heat resistivity, low hexane-extractives and controlled modulus |
US5986028A (en) * | 1991-10-15 | 1999-11-16 | The Dow Chemical Company | Elastic substantially linear ethlene polymers |
US6025448A (en) * | 1989-08-31 | 2000-02-15 | The Dow Chemical Company | Gas phase polymerization of olefins |
US6265506B1 (en) | 1997-06-09 | 2001-07-24 | The B. F. Goodrich Company | Method for the preparation of copolymers of ethylene/norbornene-type monomers with cationic palladium catalysts |
US6495760B1 (en) * | 1999-04-03 | 2002-12-17 | Pirelli Cevi E Sistemi S.P.A, | Self-extinguishing cable with low-level production of fumes, and flame-retardant composition used therein |
US6506867B1 (en) | 1991-10-15 | 2003-01-14 | The Dow Chemical Company | Elastic substantially linear ethylene polymers |
US6538080B1 (en) | 1990-07-03 | 2003-03-25 | Bp Chemicals Limited | Gas phase polymerization of olefins |
US6548611B2 (en) | 1991-10-15 | 2003-04-15 | Dow Global Technologies Inc. | Elastic substantially linear olefin polymers |
AU777541B2 (en) * | 1999-04-03 | 2004-10-21 | Prysmian Cavi E Sistemi Energia S.R.L. | Self-extinguishing cable with low-level production of fumes, and flame-retardant composition used therein |
US20100003435A1 (en) * | 2006-11-20 | 2010-01-07 | Harry Oysaedm | Article |
US20100009156A1 (en) * | 2006-12-21 | 2010-01-14 | Hans Georg Daviknes | Film |
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US20100304062A1 (en) * | 2006-12-21 | 2010-12-02 | Hans Georg Daviknes | Film |
US20110028665A1 (en) * | 2007-12-05 | 2011-02-03 | Borealis Technology Oy | Polymer |
US20110132864A1 (en) * | 2007-08-10 | 2011-06-09 | Borealis Technology Oy | Article |
US20110162869A1 (en) * | 2008-07-10 | 2011-07-07 | Annika Smedberg | Process for producing a polymer and a polymer for wire and cable applications |
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JP2814715B2 (en) * | 1990-07-24 | 1998-10-27 | 日立電線株式会社 | Electric wires and cables |
IN2012DN03433A (en) | 2009-11-11 | 2015-10-23 | Borealis Ag | |
EP2499176B2 (en) | 2009-11-11 | 2022-08-10 | Borealis AG | Power cable comprising a polymer composition comprising a polyolefin produced in a high pressure process |
JP5739442B2 (en) | 2009-11-11 | 2015-06-24 | ボレアリス エージー | Cable and its manufacturing method |
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- 1984-12-20 EP EP84308950A patent/EP0150610B1/en not_active Expired
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US5179171A (en) * | 1985-05-24 | 1993-01-12 | Mitsui Petrochemical Industries, Ltd. | Random copolymer, and process for production thereof |
US5658998A (en) * | 1985-05-24 | 1997-08-19 | Mitsui Petrochemical Industries, Ltd. | Random copolymer, and process and production thereof |
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US6025448A (en) * | 1989-08-31 | 2000-02-15 | The Dow Chemical Company | Gas phase polymerization of olefins |
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US5792534A (en) | 1994-10-21 | 1998-08-11 | The Dow Chemical Company | Polyolefin film exhibiting heat resistivity, low hexane extractives and controlled modulus |
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US5677405A (en) * | 1995-05-24 | 1997-10-14 | The B.F. Goodrich Company | Homopolymers and copolymers of cationically polymerizable monomers and method of their preparation |
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Also Published As
Publication number | Publication date |
---|---|
EP0150610A3 (en) | 1985-08-28 |
EP0150610A2 (en) | 1985-08-07 |
EP0150610B1 (en) | 1989-04-19 |
JPS60133042A (en) | 1985-07-16 |
DE3477861D1 (en) | 1989-05-24 |
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